Non plateout molding composition

ABSTRACT

A novel molding composition is described which prevents plateout of pigment on the surface of a mold or shaping apparatus during the molding or shaping operation. The composition has improved thermal and oxidation stability as well as increased compatibility of the components of the composition. The composition comprises a thermoplastic resin, a fluorescent pigment, a metal salt or complex, polymer or oligomer reagent containing a reactive functionality and other conventional additives. The composition is useful in preparing such molded articles as films, bottles, closures, furniture and toys.

This is a continuation of co-pending application Ser. No. 07/299,141filed on Jan. 20, 1989 now abandoned, which is a divisional ofco-pending application Ser. No. 055,421 filed on May 28, 1987 now U.S.Pat. No. 4,820,760.

BACKGROUND OF THE INVENTION FIELD OF THE INVENTION

This invention relates generally to a molding composition for inhibitingplateout of pigment on the surface of a mold or shaping apparatus duringthe molding or shaping operation. The composition also exhibits highcompatibility of its components and improved thermal and oxidationstability. The molding composition of the invention comprises athermoplastic resin, a reagent containing a reactive functionality, afluorescent pigment and a metal salt or complex.

STATE OF THE ART

The pigmenting of thermoplastic resins, which are used to prepare moldedarticles by various molding and shaping processes, is well known.However, there have been numerous problems associated with preparingsuch molded articles from pigmented thermoplastics. For example,pigments are generally chemical compounds of radically distinctstructure and chemistry from that of the thermoplastic resin to whichthe pigment is added. Therefore, the pigment is often times incompatiblewith the thermoplastic resin and this, in turn, creates problems ofnon-uniform dispersability within the thermoplastic resin moldingcomposition as well as resulting in the pigment rising to the surface ofthe thermoplastic resin during the molding or shaping process. If thepigment does rise to the surface, it may adhere to the wall of the moldduring the formation of the particular article. This phenomenon isreferred to as "plateout". If this occurs, the resultant molded articlewill not have the desired uniformity and pigmentation. Also, withcontinuous use of the mold, the pigment will build up on the surface ofthe mold which, in turn, requires down-time of the molding apparatus inorder to clean the mold surface.

Many of the problems associated with pigmenting thermoplastic resins foruse in the preparation of molded articles have been satisfactorilyresolved. For example, in U.S. Pat. No. 3,462,388 fluorescent compoundbonded polymers, which can be molded or spun into filaments, aredisclosed. It is disclosed in the patent that the fluorescent compoundsare chemically bonded to the polymer to produce the desired properties.

U.S. Pat. No. 3,592,777 discloses a polymer blend that exhibitsfluorescence when subjected to a selected activation energy. Thepolymers are prepared from an aliphatic or aromatic substitutedaliphatic diketone and an aliphatic diamine which results in a linearnon-cross-conjugated polymer.

U.S. Pat. No. 4,331,584 discloses various styryl compounds for coloringof synthetic resins. It is disclosed that these pigments have improvedfastness to sublimation and increased pH sensitivity.

In U.S. Pat. No. 4,238,384, a method for incorporating additives inpolymer materials is disclosed. The additives include stabilizers,anti-oxidants and antistatic agents. An optical brightener isincorporated in the thermoplastic polymer, and subjected to radiation todetermine the degree of uniformity of the distribution of theadditive-brightener blend.

U.S. Pat. No. 4,626,565 discloses a process for the preparation ofpolypropylene-based resin compositions. The composition is suitable foruse in the preparation of such molded articles as automobile bumpers,fenders, body side members and the like. The polymers exhibit excellentlow temperature impact resistance, high molding fluidity, goodpaintability and high stiffness.

U.S. Pat. No. 3,454,676 discloses blends of ionomer resins andelastomers. These blends give molded articles having both resilience andtoughness.

U.S. Pat. No. 4,223,113 discloses polyester molding compositions whichcrystallize rapidly and thus allow lower mold temperatures along withshorter injection cycles.

U.S. Pat. No. 3,915,884 discloses various modified polyamides which areuseful matrix materials for incorporating dyes, particularly fluorescentdyes. The dye incorporated into the modified polyamide forms a pigmenthaving high heat stability.

U.S. Pat. No. 2,938,873 discloses various fluorescent pigments usefulfor pigmenting thermoplastic resins. The pigments exhibit improved lightfastness and color brightness.

U.S. Pat. No. 3,303,168 discloses thermoplastic resins and moldedarticles thereof which are pigmented with fluorescent pigments.

None of the above-discussed patents disclose techniques relating to orsolutions for the plateout problem. Furthermore, none of these patentsdisclose the unique composition of the present invention.

SUMMARY OF THE INVENTION

In accordance with the present invention, a novel molding compositionhas been developed that inhibits plateout of pigment on the surface of amold or shaping apparatus during the molding or shaping operation.Components of the composition exhibit high compatibility and alsoimproved thermal and oxidation stability.

Further, in accordance with the invention, pigmented fluorescent moldedarticles having high impact strength are provided.

Still further in accordance with the invention, a method for inhibitingplateout of pigment on the surface of a mold or polymer shapingapparatus is provided.

Still further, in accordance with the invention, a polymer moldingcomposition that effectively inhibits plateout has been discovered whichis useful in a variety of different molding and shaping processes withdifferent thermoplastic resins.

Still further in accordance with the invention, a polymer moldingcomposition in a color concentrate form for effectively inhibitingplateout is provided. The color concentrate form of the moldingcomposition is blended with the desired thermoplastic resin to prepareshaped articles.

Still further in accordance with the invention, a novel non-plateoutmolding composition is provided that exhibits improved thermal andoxidation stability as well as improved compatability of its componentsand comprises:

(A) at least one thermoplastic resin;

(B) at least one fluorescent pigment; and,

(C) at least one polymer or oligomer reagent containing a reactivefunctionality selected from the group consisting essentially of carboxyand the polyvalent metal salts thereof, hydroxy, epoxy, amino orcombinations thereof.

Still further in accordance with the invention, a novel non-plateoutmolding composition is provided that exhibits improved thermal andoxidation stability as well as improved compatability of its componentsand comprises:

(A) at least one thermoplastic resin;

(B) at least one fluorescent pigment;

(C) at least one metal salt or complex selected from the groupconsisting of metal sulfates, carbonates, silicates, oxides, chromatesand mixtures thereof; and,

(D) at least one polymer or oligomer reagent containing a reactivefunctionality selected from the group consisting essentially of carboxyand the polyvalent metal salts thereof, hydroxy, epoxy, amino orcombinations thereof.

These and other aspects of the invention will become clear to thoseskilled in the art upon the reading and understanding of thespecification.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The novel combination of components of the molding composition of thepresent invention is highly effective for inhibiting the phenomenon ofplateout on the surface of the mold or shaping apparatus for formingshaped articles. As discussed above, plateout phenomenon occurs duringthe molding or shaping process of pigmented thermoplastic resins andresults from the pigment rising to the surface of the resin and adheringto the surfaces of the mold or shaping apparatus. Build up of pigment onthe surface or wall of the mold or shaping apparatus (e.g., rollers of asheet extruder) creates numerous problems which include defects in themolded or shaped articles as well as the requirement for down time ofthe particular apparatus to clean the particular surface and, in turn,obviously affecting the economics for preparing the particular molded orshaped articles. The molding compositions of the present invention arenot only effective in inhibiting plateout but also exhibit improvedthermal and oxidation stability as well as increased compatibility ofthe various components. The resultant molded or shaped articles alsoexhibit improved impact strength.

In general, the molding composition of the present invention comprises:

(A) at least one thermoplastic base resin;

(B) at least one fluorescent pigment;

(C) at least one metal salt or complex selected from the groupconsisting essentially of metal sulfates, carbonates, silicates, oxides,chromates and mixtures thereof;

(D) at least one polymer or oligomer reagent containing a reactivefunctionality selected from the group consisting essentially of carboxyand the polyvalent salts thereof, hydroxy, epoxy, amino, or combinationsthereof; optionally,

(E) mineral oil; and, optionally,

(F) fillers and processing aids.

The polymers which are useful as the thermoplastic resin in the moldingcomposition of the present invention include most thermoplastic organicpolymers which may be processed at temperatures below the decompositiontemperatures of any of the components of the composition. Such polymersinclude polyamides, polyesters, polyurethanes, polyacrylates,polyacrylonitrile, ABS copolymers, polystyrenes, polycarbonates,polyvinylchloride, and polyolefins, particularly low density, linear lowdensity and high density polyethylene and polypropylene and theircopolymers. It is intended that the above listed polymer systems includehomopolymers and copolymers. High density polyethylene is preferred forthe purposes of the present invention. However, it is pointed out thatthe particular molded or shaped articles to be prepared as well as themolding or shaping process employed to prepare the particular moldedarticle will be factors in determining the selection of the particularthermoplastic resin to be used in the molding composition of theinvention.

Pigments and/or dyes useful in formulating the molding composition ofthe present invention are preferably fluorescent materials. Suchmaterials include both organic, and inorganic compounds and may befluorescent dyes, fluorescent pigments and the intermediates offluorescent dyes and pigments. Such dyes or pigments will generallyinclude the colors of red, orange, yellow, pink, green or blue.Exemplary of such fluorescent materials which may be used in thecomposition according to the present invention are modified polyamidesmade from a co-condensation product of: (a) a polyfunctional primaryamine, preferably a difunctional amine; (b) a monocarboxylic aromaticacid, preferably benzoic acid or a substituted carboxy benzene; (c) apolycarboxylic aromatic acid, preferably a dicarboxylic aromatic acidwith carboxy groups on noncontiguous carbon atoms, and optionally (d) anepoxy resin which will not destroy the thermoplastic characteristics ofthe co-condensation product, preferably one based on bisphenol A, suchthat at least one carboxy group remains on the majority of the moleculesof the co-condensate. More particularly, the material consists of apigment made from the modified polyamide described above and a coloringmaterial, preferably one which is compatible with the modified polyamideand preferably one which is characterized by an ability to fluoresce inthe presence of ultraviolet or blue-green light. Thus, the pigment maybe obtained by the preparation of a co-condensate of (a) (b) (c) and(d), which may include a coloring material, and particularly a daylightfluorescent dye. The ratio of a:b:c may vary widely provided at leastone carboxy group remains on the majority of the molecules of thecondensate, and the average molecular weight is not substantially inexcess of 2500. The molar ratio of a:b:c ranges from about 10:1:10 toabout 1:1:1; most preferred are ratios of a:b:c from about 4:1:4 toabout 1:1:1. Preferred molar ratios of a:b:c:d range from about 3:3:4:1to about 1:13:17:6.

In another embodiment the pigment material consists of a co-condensationproduct of: (a) a polyfunctional primary amine, preferably adifunctional amine; (c) a polycarboxylic aromatic acid, preferably adicarboxylic aromatic acid with a carboxy group on noncontiguous atoms,chosen in such a ratio as to provide at least one carboxy groupremaining on the majority of the molecules of the co-condensate. Acoloring material of a fluorescent dye may be added to the co-condensateto form a pigment. The ratio of a:c may vary widely provided at leastone carboxy group remains on the majority of the molecules of theco-condensate and the average molecular weight is not substantially inexcess of 2500. The molar ratio of a:c is always greater than 1:1 butnot greater than 1:2.

The above pigments are described in U.S. Pat. No. 3,915,884 which isexpressly incorporated herein by reference for such disclosure.

Other suitable pigment materials useful in the molding process of thepresent invention are thermoplastic resins that may be formed from anaromatic monosulfonamide having two reactive amide hydrogens, a cyclicaminotriazine having at least two primary amino groups and formaldehydeor paraformaldehyde. If desired either or both of the first mentionedcomponents may be separately reacted with formaldehyde to form athermoplastic sulfonamide-aldehyde resin or a B-stage (partiallycondensed) aminotriazine-aldehyde resin, respectively, before beingco-condensed. The aromatic sulfonamide may comprise toluene sulfonamide,e.g., o- or p-toluene sulfonamide or mixtures thereof, benzenesulfonamides, or the alkyl derivatives of such sulfonamides, and thelike, in which the sulfonamido group is attached directly to thearomatic nucleus through the sulfur atom. These pigment materials aredescribed in U.S. Pat. Nos. 2,938,873 and 3,303,168 which are expresslyincorporated herein by reference for such disclosure.

Suitable polymer or oligomer reagents for the purposes of the presentinvention are materials which contain a reactive functionality that isreactive with various plateout substances that may be present in themolding composition or that may be produced during the molding orshaping process. Such functionalities include carboxy and the polyvalentmetal salts thereof, hydroxy, epoxy, amino and combinations thereof.Materials containing these fucntionalities include such polymers andoligomer materials as ionomer resins, fatty acids, the salts and dimeracids thereof, polyamines, fatty acid epoxides, glycidyl and diglycidylethers and the like.

Ionomer copolymers or resins useful in the present invention arecopolymers of an α-olefin and an ethylenically unsaturated carboxylicacid. These copolymers are referred to as ionomers because of theirionic character which is obtained by neutralizing with metal ions atleast a portion of the free acid groups in the copolymer. These resinsare described, for example, in U.S. Pat. No. 3,454,676 which disclosureis expressly incorporated herein by reference for the disclosure ofthese resins. For the purposes of the present invention, a preferredionomer resin is of the Surlyn™ type manufactured by DuPont. Usefulmetal ions, include those having an oxidation state of 1-3 inclusive,and particularly those of Group I (a and b) and Group II (a and b) aswell as the transition metals of the Periodic Table. For the purposes ofthe present invention, zinc is preferred. Examples of olefins which maybe used to prepare the ionomer resin of the present invention includeethylene, propylene, butene-1 and hexene-1. Examples of ethylenicallyunsaturated carboxylic acids useful in preparing the ionomer resins ofthe present invention include acrylic and methacrylic acids, maleic andfumaric acids and the monoalkyl esters and anhydrides thereof.Copolymers of ethylene and acrylic acid or methacrylic acid arepreferred.

Suitable fatty acid reagents include oligomers and dimers of such acidsas stearic, oleic, dodecanoic, eicosonic, and the like. The polyvalentmetal salts of these carboxylic acids may also be used and in someinstances may be preferred, e.g., the zinc salt of stearic acid. Alsovarious polymers and copolymers of maleic acid and maleic anhydride maybe used. For example, copolymers of styrene-maleic anhydride,ethylene-maleic anhydride, ethylene, propylene-maleic anhydride,ethylene; vinyl acetate-maleic anhydride and the like may be used.

The polyamines which may be useful in the present invention includevarious alkylene, aromatic,substituted and unsubstituted polyamines ofsuch amines as benzylamine, hexylamine, propylamine, diethanol amine,triethanol amine, ethylene diamine, diethylenetriamine, hexamethylenediamine and the like. Also polymers and copolymers of heteroatom aminessuch as oxazolines, and the like may be employed.

Illustrative epoxides, which polymers and oligomers thereof are usefulin accordance with the invention include various fatty acid typeepoxides as well as glycidyl and diglycidyl ethers. Exemplary of suchepoxides are 1-octene oxide, 2-octene oxide, 1-dodecene oxide,1-hexadecene oxide, 1-eicosene oxide, butyl epoxystearate, commercialmixtures of C₁₂₋₁₈ straight chain α-olefin epoxides, glycidyl ethers ofglycerol, glycidyl ethers of tetrakis (hydroxy phenyl) ethane and thelike.

With respect to the metal salts or complexes, as discussed above, the,particular salt or complex must be capable of absorbing, adsorbingand/or reacting with plateout materials present in the moldingcomposition. Such plateout materials that may be present in the moldingcomposition or formed during the molding or shaping operation, includelow molecular weight amines, amides, polyamines and polyamides. Metalsalts or complexes useful for the molding composition of the presentinvention include metal sulfates, metal carbonates, metal silicates,metal oxides, metal chromates and mixtures thereof. These materials willbe present in the molding composition in an amount sufficient toabsorb/adsorb and/or react with plateout materials in the moldingcomposition or formed during the molding or shaping process. Thematerials may also serve the dual function of providing good moldrelease property at the conclusion of the molding or shaping operation.Preferred metal salts or complexes include alkaline earth sulfates,carbonates or oxides, iron oxides, sulfates or carbonates, titaniumoxides, tin oxides and mixtures thereof. Such salts specifically includeBaSO₄, ZnO, MgO, CaO, CaCO₃ and CaSO₄. The most preferred is bariumsulfate for the purposes of the present invention.

Mineral oil may be employed in the molding composition of the inventionas an encapsulating or wetting agent.

The molding composition of the present invention may also include otherart recognized additives for plastic molding compositions which may beused in a variety of molding processes. Such other additives includefillers and processing aids. Specifically, such materials include talc,clay, glass powder, dolomite, diatomaceous earth, titanium dioxide andthe like. Furthermore, flame retardant agents, antioxidants, antistaticagents, mold release agents and the like may also be added to thecomposition.

For the purposes of the present invention, the thermoplastic resins willbe present in the molding composition in an amount sufficient to producea well dispersed encapsulated pigmented pellet form and to give adimensionally stable molded article having sufficient impact strength.Preferably, this amount will range from about 20% to about 80% by weightin preparing the color concentrate molding composition to be blendedwith virgin thermoplastic resin. If the particular thermoplastic resinis a high density polyethylene, the preferred amount of thethermoplastic resin in the color concentrate molding composition of thepresent invention is about 40% by weight. The fluorescent pigment ispresent in an amount to give the desired opacity, color andfluorescence. For the purposes of the present invention, this amountwill preferably be in the range of about 15% to about 45% by weight forthe concentrate molding composition. The metal salt or complex, aspointed out above, may be present in an amount sufficient to absorb,adsorb and/or react with plateout materials present in the compositionor formed during the molding or shaping operation. In general thisamount will range from about 5% to about 20% by weight of theconcentrate molding composition and preferably about 10% by weight ifthe particular metal salt is barium sulfate. The polymer or oligomerreagent will be present in an amount sufficient to inhibit plateout ofthe pigment. This amount will generally range from about 1% to about 25%by weight and if an ionomer resin is employed, the amount willpreferably range from about 5% to about 18%. If mineral oil is presentin the composition, it will range from about 0% to about 3% by weightand is most preferably present in an amount of about 1% by weight. Theremaining fillers and/or processing agents will be present in amount ofup to about 25% by weight of the concentrate molding composition andwill make up the balance of the composition depending upon the amountsof the other components added to the composition. The above relativeamounts given for each of the respective components of the compositionhave been determined to give a molding composition which is highlyeffective in preventing plateout of pigment on the mold or shapingsurface as well as giving improved thermal and oxidation stability andincreased compatibility of the particular components making up thecomposition. It should be clear to one skilled in the art that specificamounts of each component will vary depending on the specific materialused to formulate the molding composition as well as the specific moldedor shaped article to be prepared and the particular molding or shapingprocess to be utilized.

The above described color concentrate molding composition may beformulated in any desired physical form to be blended with unformulatedthermoplastic resins and processed into a molded or shaped article. Itwill be recognized by one skilled in the art, however, that for mostmolding and/or shaping processes, pellets of the concentrate are mostadvantageous for accommodating most molding and shaping apparatuses orprocesses, e.g., injection molding, extrusion molding or shaping, blowmolding and the like. Moreover, the various components of the moldingcomposition of the invention may be compounded directly with theparticular thermoplastic resin in the appropriate concentration rangefor molding. This is opposed to preferably first preparing a concentratefor dilution with virgin thermoplastic resin.

Components of the molding composition may be added in a single batch andblended or alternatively the polymeric reagent containing a reactivefunctionality and the pigment may be first blended together andsubsequently added to the other components to make up the balance of thecomposition. The thus formed color concentrate molding composition willbe blended with virgin thermoplastic resin in an amount sufficient togive the desired strength, opacity, coloration, i.e., pigment loading,and other such properties desired for the article to be formed.Generally, this amount will range in a ratio from about 100 to 1 toabout 10 to 1 of virgin resin to the color concentrate according to theinvention. This blend ratio results in an approximate pigmentconcentration in the blend of about 1% to about 10% by weight of thetotal blend. In a more preferred embodiment of the invention, the blendratio will vary from about 50 to 1 to about 10 to 1 and in a mostpreferred embodiment this ratio will vary from about 35 to 1 to about 20to 1 of the virgin resin to the color concentrate. This blendcomposition may then be utilized to prepare a variety of differentmolded or shaped articles by various molding and shaping processes. Forexample, such molded articles as fibers and films may be prepared fromthis molding composition as well as specific articles such as bottles,closures, transition parts of bottles, toys, furniture and cabinets forvarious electronic equipment and the like. These molded articles may beprepared by such processes as injection molding, injection blow molding,sheet extrusion, film extrusion, blow molding, thermoforming and thelike. For example, closures, toys and furniture may be prepared byinjection molding. Bottles are prepared by injection blown moldingtechniques and plastic bags are prepared from blow film.

Various molding compositions representative of compositions within thescope of the present invention are illustrated in the followingexamples. While these examples will show one skilled in the art how tooperate within the scope of this invention, they are not to serve as alimitation on the scope of the invention for such scope is defined onlyin the claims. It is pointed out that in the following examples, andelsewhere in the present specification and claims, all percentages andall parts are intended to express percent by weight and parts by weightunless otherwise clearly indicated.

EXAMPLE I

A color concentrate molding composition according to the presentinvention was formulated as follows:

5%--TiO₂

19%--strong fluorescent yellow pigment from Day-Glo Color Corp.

14%--strong fluorescent orange pigment from Day-Glo Color Corp.

46%--high density polyethylene (HDPE)

11%--BaSO₄

5%--Zinc based SURLYN™.

The above color concentrate composition was pelletized and blended withvirgin high density polyethylene (HDPE) in a ratio of 25 to 1 (HDPE tothe concentrate).

EXAMPLE II

A color concentrate molding composition according to the presentinvention was formulated as follows:

25%--strong fluorescent yellow pigment from Day-Glo Color Corp.

5%--TiO₂

5%--Zn based SURLYN™

10%--BaSO₄

1%--Calcium Stearate

53%--HDPE

1%--mineral oil.

The above color concentrate composition was pelletized and blended withvirgin high density polyethylene (HDPE) in a ratio of 25 to 1 (HDPE tothe concentrate).

EXAMPLE III

A color concentrate molding composition according to the presentinvention was formulated as follows:

28%--strong fluorescent orange pigment from Day-Glo Color Corp.

11%--strong fluorescent orange pigment from Day-Glo Color Corp.

4%--TiO₂

10%--BaSO₄

5%--Zn Based SURLYN™

42%--HDPE.

The above color concentrate composition was pelletized and blended withvirgin high density polyethylene (HDPE) in a ratio of 33 to 1 (HDPE tothe concentrate).

EXAMPLE IV

A color concentrate molding composition according to the presentinvention was formulated as follows:

11%--TiO₂

14%--strong fluorescent orange pigment from Day-Glo Color Corp.

7.5%--strong fluorescent orange pigment from Day-Glo Color Corp.

9%--BaSO₄

5%--HDPE

4.5%--Zn Based SURYLN™.

The above color concentrate composition was pelletized and blended withvirgin high density polyethylene (HDPE) in a ratio of 33 to 1 (HDPE tothe concentrate).

EXAMPLE V

A color concentrate molding composition according to the presentinvention was formulated as follows:

33%--strong fluorescent orange pigment from Day-Glo Color Corp.

4%--Cadmium pure light red pigment from Ferro Corp.

4%--Cadmium red pigment from Ferro Corp.

5%--TiO₂

10%--BaSO₄

5%--Zn Based SURYLN™

1%--mineral oil

38%--HDPE.

The above color concentrate composition was pelletized and blended withvirgin high density polyethylene (HDPE) in a ratio of 20 to 1 (HDPE tothe concentrate).

Plastic plaques were prepared by injection molding techniques from themolding composition blends of Examples I-V described above. The moldswere then examined for plateout by the following procedure.

All the Example compositions contained 3000 gms. of blow mold gradeHDPE. The plaques were prepared at an injection blow molded at atemperature of 410°-425° with a 30 sec. cycle.

The mixture of HDPE and concentrate is run on the injection moldingmachine for one hour.

Both sides of the mold are visually examined for any build-up, colorbuild-up, non-colored build-up, waxy or crystalline characteristics,odor and the like.

A white cotton cloth or tissue paper is soaked in rubbing alcohol, and astraight line smear is made on the mold cavity and on the flat back ofthe mold.

The level of plateout is then subjectively evaluated using a 1 to 10scale:

0--No plateout on the mold, and no color or chemical residue on smearedcloth.

10--Infinite plateout on the mold, and color or chemical residue onsmeared cloth.

If the plateout is between the scale of 0-3, the product will pass as anon-plateout color concentrate.

All the above molding compositions of Examples I-V passed this procedurefor non-plateout.

While the invention has been described and illustrated above withreference to a specific preferred embodiment thereof, those skilled inthe art will appreciate the various changes, modifications andsubstitutions made therein without departure from the spirit of theinvention. For example, various amounts for each of the components andspecific materials used for each of the components of the moldingcomposition other than the preferred amounts or materials set forthhereinabove may be applicable as a consequence of the nature of thevarious components employed in the process and such other expectedvariations or differences and results are contemplated in accordancewith the practices of the present invention. It is intended, therefore,that the invention be limited only by the scope of the claims whichfollow.

We claim:
 1. A method for inhibiting plateout on the surface of the moldduring the preparation of a molded or shaped article comprising:(1)intimating blending a composition comprising:(A) at least one moldablethermoplastic resin selected from the group consisting of ethylenepolymers and copolymers, propylene polymers and copolymers,acrylonitrile polymers and copolymers, polymers and copolymers ofacrylic acid, methacrylic acid and their esters; (B) at least onefluorescent pigment; and an effective amount of plateout inhibitingagents comprising: (C) at least on metal salt or complex selected fromthe group consisting of metal sulfates, carbonates, silicates, oxides,chromates and mixtures thereof in an amount sufficient to inhibitplateout; and (D) at least one polymer or oligomer reagent containing areactive functionality reactive with plateout substances present orproduced during the molding process and selected from the groupconsisting of carboxy and the polyvalent metal salts thereof, hydroxy,epoxy, amino and combinations thereof; and (2) molding or shaping saidcomposition at the molding or shaping temperature for said thermoplasticresin to form said molded or shaped article.
 2. The method according toclaim 1 wherein said molded or shaped article is prepared by a moldingor shaping process selected from the group consisting of blow molding,injection molding, sheet extruding, blown films and film extruding. 3.The method according to claim 2 wherein said molding process isblow-molding.
 4. The method according to claim 1 wherein:saidthermoplastic resin is selected from the group consisting of ethylenepolymers and copolymers, propylene polymers and copolymers,acrylonitrile polymers and copolymers, polymers and copolymers ofacrylic acid, methacrylic acid and the esters thereof and polyesters. 5.The method according to claim 4 wherein said thermoplastic base resin ishigh density polyethylene.
 6. The method according to claim 1 whereinsaid composition comprises:(A) high density polyethylene; (B) afluorescent orange pigment; (C) BaSO₄ ; and, (D) a zinc based ionomerresin.
 7. The method according to claim 1 wherein said compositionfurther comprises mineral oil, a filler and processing aids.
 8. Themethod according to claim 1 wherein said molding composition is preparedin the form of a concentrate and said components comprise the followingrelative amounts of the concentrate:(A) is present in an amount rangingfrom about 20% to about 80% by weight; (B) is present in an amountranging from about 15% by weight to about 45% by weight; (C) is presentin an amount ranging from 0% to about 20% by weight; and, (D) is presentin an amount ranging from about 1% to about 25% by weight.
 9. Afluorescent molded article having high impact strength prepared from anon-plateout molding composition comprising:(A) at lest one moldablethermoplastic resin selected from the group consisting of ethylenepolymers and copolymers, propylene polymers and copolymers,acrylonitrile polymers and copolymers, polymers and copolymers ofacrylic acid, methacrylic acid and their esters; (B) at least onefluorescent pigment; and an effective amount of plateout inhibitingagents comprising: (C) at least one metal sale or complex selected fromthe group consisting of metal sulfates, carbonates, silicates, oxides,chromates and mixtures thereof in an amount sufficient to inhibitplateout; and, (D) at least one polymer or oligomer reagent containingat least one reactive functionality reactive with plateout substancespresent or produced during the molding process and selected from a groupconsisting essentially of carboxy and the polyvalent metal saltsthereof, hydroxy, epoxy, amino and the combinations thereof.
 10. Themolded article according to claim 9 wherein said thermoplastic resin isselected from the group consisting of ethylene polymers and copolymers,propylene polymers and copolymers, acrylonitrile polymers andcopolymers, polymers and copolymers of acrylic acid, methacrylic acidand the esters thereof, and polyesters.
 11. The molded article accordingto claim 10 wherein said thermoplastic resin is high densitypolyethylene.
 12. The molded article according to claim 9 wherein saidmolding resin comprises:(A) high density polyethylene; (B) a fluorescentorange pigment; (C) BaSO₄ ; and, (D) a zinc based ionomer resin.
 13. Themolded article according to claim 9 wherein said molding composition isprepared in the form of a concentrate and said components comprise thefollowing relative amounts of the concentrate:(A) is present in anamount ranging from about 20% to about 80% by weight; (B) is present inan amount ranging from about 15% by weight to about 45% by weight; (C)is present in an amount ranging from 0% to 20% by weight; and, (D) ispresent in an amount ranging from about 1% to about 25% by weight. 14.The molded article according to claim 9 wherein said article is anextruded film.
 15. The molded article according to claim 9 wherein saidarticle is a bottle.
 16. The molded article according to claim 15wherein said bottle is formed by blow molding and said thermoplasticresin is high density polyethylene.
 17. The method according to claim 8wherein said color concentrate is blended with a virgin thermoplasticresin in a ratio of about 100 to 1 to about 10 to 1 of virginthermoplastic resin to color concentrate.
 18. The method according toclaim 17 wherein said thermoplastic resin is high density polyethyleneand said ratio ranges from about 50 to 1 to about 10 to
 1. 19. Themethod according to claim 18 wherein said ratio ranges from about 35 to1 to about 20 to 1.